Liquid phase fluorination

Abstract

This invention pertains to a method for liquid phase fluorination for perfluorination of a wide variety of hydrogen-containing compounds.

We claim: 
     
       1. A liquid-phase process for forming a perfluorinated organic substance without the addition of a hydrogen fluoride scavenger which comprises directly contacting in a temperature-controlled reactor a diluted solution or dispersion of a perfluorinateable, organic substance in a liquid, inert medium with a stoichiometric excess of fluorine gas, optionally diluted with an inert gas, to perfluorinate said organic substance using a temperature in the range of between about -40° and 90° C. and a flow rate of the inert gas and the fluorine gas sufficient to volatilize and remove the resulting byproduct hydrogen fluoride from the reactor, removing said hydrogen fluoride from the reactor as it is produced, and separately removing from the reactor the resultant solution or dispersion of said perfluorinated organic substance. 
     
     
       2. The method of claim 1, wherein the organic substance is an ether or polyether having 5 to 10,000 carbon atoms. 
     
     
       3. The method of claim 1, wherein the ether is a linear polyether. 
     
     
       4. The method of claim 1, wherein the organic substance is a chlorinated organic compound. 
     
     
       5. The A method of claim 4, wherein the organic substance is a telomer of polyvinylchloride. 
     
     
       6. The method of claim 1, wherein the organic substance is a polyaromatic hydrocarbon. 
     
     
       7. The method of claim 6, wherein the organic substance is polystyrene. 
     
     
       8. The method of claim 1, wherein the organic substance is a monocyclic or polycyclic aromatic compound having 6 to 30 carbon atoms. 
     
     
       9. The method of claim 1, wherein the organic substance is a hydrocarbon polymer having 10 to 10,000 carbon atoms. 
     
     
       10. The method of claim 1, wherein the organic substance is a cyclic ether having more than 10 carbon atoms. 
     
     
       11. The method of claim 1, wherein the liquid, inert medium is a perhalogenated chlorofluorocarbon. 
     
     
       12. The method of claim 11, wherein the perhalogenated chlorofluorocarbon is 1,1,2-trichlorotrifluoroethane. 
     
     
       13. The method of claim 11, wherein the perhalogenated chlorofluorocarbon is a perhalogenated chlorofluoropolyether. 
     
     
       14. The method of claim 11, wherein the perhalogenated chlorofluoropolyether is   (CF.sub.2 Cl).sub.2 CFOCF.sub.2 OCF(CF.sub.2 Cl).sub.2.     15.   
     
     
       15. The method of claim 11, wherein the perhalogenated chlorofluorocarbon is   CF.sub.2 ClCF.sub.2 OCF.sub.2 OCF.sub.2 CF.sub.2 Cl.     
     
     
       16. The method of claim 1, wherein the liquid, inert medium is the essentially perfluorinated compound. 
     
     
       17. The method of claim 11, wherein the organic substance is first dissolved in a solvent and is then introduced into the liquid, inert medium in solution. 
     
     
       18. The method of claim 17, wherein the solvent does not consume fluorine. 
     
     
       19. The method of claim 17, wherein the solvent is the same liquid as the liquid medium. 
     
     
       20. The method of claim 1, wherein the organic substance is insoluble in the liquid fluorination medium and is introduced into the medium to form a suspension or emulsion. 
     
     
       21. The method of claim 20, wherein the emulsion or suspension is formed continuously in the reactor as the fluorination reaction proceeds. 
     
     
       22. The method of claim 1, wherein the perfluorination is carried out at a temperature in the range of about -10° C. to 50° C. 
     
     
       23. The method of claim 1, wherein the perfluorination is carried out in a batch or continuous mode. 
     
     
       24. The method of claim 1, wherein the organic substance is extracted with liquid perhalogenated chlorofluorocarbon or chlorofluoroether medium wherein the extracted organic substance is then fluorinated. 
     
     
       25. A liquid-phase process for forming a perfluorinated organic substance without the addition of a hydrogen fluoride scavenger comprises introducing a perfluorinateable organic substance into a temperature-controlled reactor having an agitated liquid, inert medium to form a diluted solution or dispersion of the perfluorinateable, organic substance in the liquid, inert medium, introducing a stoichiometric excess of fluorine gas, optionally diluted with an inert gas, while in the absence of a hydrogen fluoride scavenger, to perfluorinate said organic substance using a temperature in the range of between about -40° and 90° C. and a flow rate of the inert gas (if used) and the fluorine gas sufficient to volatilize and remove the resulting byproduct hydrogen fluoride from the reactor, thereby forming the perfluorinated organic substance, removing said byproduct hydrogen fluoride from the reactor as it is produced, and separately removing from the reactor the resultant solution or dispersion of said perfluorinated organic substance. 
     
     
       26. A liquid-phase process for forming a perfluorinated organic substance without the addition of a hydrogen fluoride scavenger which comprises directly contacting in a temperature-controlled reactor a diluted solution or dispersion of a perfluorinateable, organic substance in a liquid perhalogenated chlorofluorocarbon medium with a stoichiometric excess of fluorine gas, optionally diluted with an inert gas, to perfluorinate said organic substance using a temperature and a flow rate of the inert gas (if used) and the fluorine gas sufficient to volatilize the resulting byproduct hydrogen fluoride and remove it from the reactor, removing said hydrogen fluoride from the reactor as it is produced, and separately removing from the reactor the resultant solution or dispersion of said perfluorinated organic substance. 
     
     
       27. The method of claim 1 wherein the perfluorination is carried out at a temperature in the range of about -40° C. to 70° C. 
     
     
       28. The method of claim 1 wherein the perfluorination is carried out at a temperature in the range of about -40° C. to 50° C.